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o ser* et f aniaamdi s *we est alguna, e n i ss man@ .o on sam isili lll-d A Slllilfl .lames G. diurnas' and idolatria, Scotia, and Smith, y, islii., srsignors to Fl Ecusson?, a ce" eration c" New Yori: 5, llefl, No. lll @L 2173mnel rlhis invention is concerned with compositions of inatter and their use in projection systems utilizing these compositions of matter as deformable media. More particularly, *die invention is concerned with compositions oi matter having the general formula where R is a monovalent hydrocarbon radical selected from the cale, Z is a radical selected irom the class consisting of the biobenylyl, naphthyl, and phenoftygahenyl radicals, and .u is an integer equal to from 2 to 4, inclusive. The invention also relates to the use of the aforesaid compositions of matter as the deformable medium in a projets tion system which is more particularly disclosed in US. 2,943,l137, issued lune 28, i960, aud in US. 2,391,450, issued lecember 25, 1945.

ln the aioresaid US. latent 2,943,l47, assigned to the same assignee as the present invention, there is disclosed and claimed a projection system temblor/ing a deformable medium having a high resistivity which is responsive to an electron beam which is velocity modulated. ln general, this apparatus which is illustrated in FlG'URE l of die attached drawing comprises an evacuated glass envelope l@ containing an electron gun ill for producing an electron beam i3 and reflecting it in a rectangular raster over the surface of a transparent, deformable medium l5 that is within a portion .Tipi of the transgiarent com rainer; an enlarged view o this portion of the assembly is shown in FIGURE 2. The beam E3 is preferably velocity modulated by a television signal that is applied to the deflection means (not shown) in the electron gun The deformable medium l5 has a center portion 119 of decreased thickness, coincident with the raster area of the beam 11.3, which is produced by electrons from the beam that are attracted to a conducting coating on the inner surface of the container if. These electrons also produce deformations in the surface or" the deformable medium its, the amplitudes of which are a function ot' the number or" electrons deposited by the beam llf at the various points on the surface of the medium l5. Consequently, the amplitudes of these deformations are a function of the television signal modulating electron beam E3.

These deformations are utilized to didi-act light from a light source 23 in an optical system which is illustrated as including a lens 2d that images light source 23 on the surface of medium le' through a bar and slit system 25. Another lens 29 images the slits of system 2S on the bars of another bar and a slit system 3l. in the absence of dcformations in the surface of the deformable medium. However, any deformations phase diiract the light so that it passes through the slits in the system Elli with an intensity that corresponds to the amplitudes of the deforniations and thus the amplitude of the agrulied television signal. The light passing through system 29 is imaged by a proiection lens 32S on a screen 35 after retiection from a mirror 37.

class consisting of the methyl and phenyl radi-V lli a conventional deformable medium is utilized in the illustrated system, the average charge density produces a force on the medium l5 that overcomes the surface tension from the excess medium outside the raster arca and decreases the portion l@ of medium l5 to zero thickness; under such conditions, no deformations can be formed and the system becomes inoperative until tile medium is replaced.

ln this US. Patent 2,943,l4l7, it is stated that if the medium has the property of decreasing in resistivity with decreasing thickness, portion il@ does not decrease to zero thickness under the pressure of the` charges but rather maintains a thickness the value of which is a function of the magnitude of charge density on the surface of the medium l5. With a decr,ase in resistivity, the time constaat is decreased for the passage of leakage current from the surface of the deformable medium l5 to the conducting coating 2l beneath it, resulting in increase in leakage current, which decreases the charge density on the surface of the medium, thereby relieving the pressure somewhat. Ultimately, an equilibrium condition is attained in which the pressure from the charges on the surface of the medium equals the pressure from the surface tension on the excess medium around the raster. Then the thickness at this equilibrium condition is maintained. The charge density on the surface of the medium never decreases to zero due to the leakage because it is continually being replaced by the electrons from the beam ll3.

The deformable compositions described in the aforesaid Patent US. 2,943,147 as suitable for the medium are required to be transparent, be capable of withstanding electron bombardment without significant decompositios, have a viscosity at the operating temperature (betveen about 25 C. and 150 C.) of approximately 100 to 50,5300 centistokes, and the deformable composition must not decompose the conducting coating. The rnedium must also have a resistivity that varies within the range of approximately l()M to 1011 ohms-cm., with the average resistivity at the stable thickness being approximately 1011 ohms-cm.

Among the deformable media or fluids described in this patent are, for instance, beeswax, methyl silicone uids, methylsilicone fluids containing up to 5% of phenyl silicones, methylphenyl silicones containing an average of two methyl and phenyl groups per silicon atom in which the mol ratio of methyl groups to silicon atoms is greater than 0 and less than 2, etc. However, it has been found that these deformable iiuids are not as stable as one would desire because under the influence of ai electron beam, the deformable fluid tends to increase in viscosity, and with continued use in the projection system described above, the viscosity increases to a point where gel particles begin to forni and ultimately the deformable medium gels; of course, this means that tL e apparatus can no longer be used with that particular deformable medium.

Unexpectedly, we have discovered that a group oi organic compositions of Formula l described previously, is eminently suitable as the deformable medium in the above-described projection system. Not only are sharp, viewable images of good light intensity obtained with these fluids, but also these fluids have exceptionally low vapor pressure and much greater resistance to irradiation, and therefore are more stable in the presence of the electron beam used in the aforesaid projection system. The compositions employed by us in the aforesaid projection system can be used continuously for much longer periods of time without significant change in the deformable medium, thus adding greatly to the life of the projection system.

' .and beur/.ene was removed by distillation.

uw, ed i l/ithin the scope of Forrmlla l described above, 'ille oilowing examples given by way or". illustration and not by way of limitation as to the preparation of e. large number of these compositions which oe employed as the deformable medium in the aforesaid projection system. it is to be understood where the biphenylyl or phenoxyphenyl radical is present in the composition used as the deformable medium, the phenyl radicals of he biphenylyl group and the phenoxy radical of the pherioxyphenyl group muy be ortltd, meaor parato the point of attachment in the bipiienylyl or in the phenorryplienyl radical shown ir; Fors-ruis. l. Thus, the bipbenylyi radical attziclmzents may illustrated as and the plienoxyphenyi radical attacbruens may illus- The naplithyl radical can be attached in either the or [3 positions.

EXAMPLE l was prepared as follows. oslhenylpherioxyphonylmethylchlorosilane was Erst prepared by adding a solution of 35.1 grams of o-phcnylphenol in benzene (lfi inl. of solution) to o stirred mixture of 95.6 grams of phenylmetliyidiclilorosilane in 250 ml. benzene and 39.6 grams of dry pyridine at O to 10 C. over?. period of l() minules. The mixture was stirred for an additional Z hours and thereafter iltercd. The filter cake wus washed with benzene :1nd the benene. wash was added to the filtrate The residue was then distilled under reduced pressure to yield ll3 grams of o product boiling7 at 14S-156 @Jill rum., which was identified :is o-plienylplicnoxypiienylrnethylchlorosilarie. About 65 grams of this latter chlorcsilane was dissolved in l() ml. of benzene and to this was added 1.8 grams of water (sullicient to hydrolyze completely tlle silicon-bonded chlorine) in 15.8 ml. pyridine over a period of 2 hours at a temperature of 20-30" C. The mixture was stirred for 18 hours, liltered and the filter czilie washed with benzene. The benzene wash and the tiltrate were combined and fracionally distilled to remove benzene und lo yield o residue which distilled at 259-260 C./0.l mm. Fliiis composition was identified as having the formula by tbe fact that it was found to contain 77.0% carbon, 5.9% hydrogen and 9.7% silicon, as contrasted to the theoretricril values of 76.72% carbon, 5.76% hydrogen and 9.44% silicon.

More particularly, lll grams ot' diphcnylsilariediol was added in small portions over 21 period of 20 rninules to o. mixture of 33.7 grams of o-phenylpnenoxyplrenylmehylclilorosilane (prepared in accordance with the directions in Example l) dissolved in ml. benzene und l() mi. pyridioe. The temperature during this sddiion was kept at around 20-30" C. After allowing the resulting mix ture to stand with stirring for about lll hours, the product was ltered, the benzene removed from the Filtrate by distillation, and the residue then fractionally distilled under reduced pressure to yield a product having a boiling sint of 27?276o 70.05 mm. This material was 'found to be the composition identified by Formula lili evidenced by the fact that it contained 75.9% carbon, 5.9% hydrogen, and 10.2% silicon. as contrasted to the theoretical values of 75.71% carbon, 5.59% hydrogen, and 10.62% silicon.

EXMLE 3 Cla CH3 (24H5 O-Sl-O-Sl-O-Si-O Hg H5 H5 wm prepared as follows. intermediate cblorosilarle required, namely o-'oiplienylyloxypileuylngetbylcmoro lone, was prepared in accordance with the method de-r scribed in Example l. This o-biplieuylyloxypenylrr ylclaiorosilane was their hydrolyzed by adding i3@ gra is of this material lo e mixture of grams of sodium bi carbonate in 400 rnl. acetone held a temperature i5 io -2 C. Addition was completed in l5 minutes aud stirring of the mixture was continued for an additional .hour at tbe same temperature. T resuling mixture iiltered and :gv/tone removed under reduced pressure room temperzi The resulting mi2-:ture was their subjected to a reduced pressure of 0.5 mm. at room teuru peroture. This nydrolyzsre (which was o-biplienylyl oxyrnethylphenylsilanoll was added over e period or l5 minutes to a solution of 25.8 grams dirncliiy1dicblorosilane and 31.6 grams pyridine and 200 inl. benzene at O-l0 C. The mixture was stirred for approximately 8 hours and thereafter allowed to warm up to room temperature. The benzene was removed .aud the product fractionally distilled under reduced pressure to yield o liquid boiling at 25l-27f. C/(lQS mm., nD2U=l.5l'76. This' composiion was tiren stirred with solid soo rrr bicarbonate to remove small amounts of urircaetecl chloro silanes and thereafter 'die sodium bicarbonate was re moved and the product fractionally distilled to yield e corrigositiou boiling at 248-266 C./0.08 nini., rzD20=l.59Ol. This material which had :i viscosity :it 25" C. of 900 centistoiies was identlled :is the above-identidad edades-.t

composition leaving formula iV as evidenced by the i'act that it was found to contain 73.5% carbon, 6.3% lay- The composition 1,3-di(mphenonypbenoxy)-t,3diphenyl-l,S-dimetbyldisiloxane having tile formula was prepared as follows. lne cblorosiloziane intermediate, namely, eblorometbylpbenyldisiloaane having the formula "JI 06H15 C @He was prepared by adding i3 grams of water over a 3 hour period to a stirred solution of 709 grams metiiylpilenyldicblorosilane in an equal weight ot dietliyl etaer at 10 C. Ether was evaporated and tbe product was fractionaliy distilled onder reduced pressure to yield the above clitorosiloxane product boiling at 1Z0-421.15 C./0.02 nim. About 65.4 grams oi the aforesaid clilorometbylpieayidisiloxane was added dropvvise over a 2 hour period to a reaction vessel containing 88.4 grams tri-phenomphenol and 34.8 grams pyridine in 20G ml. benzene as solvent. After beating the mir-:ture o ingredients at the redux temperature of tlie mass for 2 hours, the pyridine hydrochloride was filtered oii' and washed with benzene. The solvent was removed from tbe ltrate and distillation under reduced pressure yielded lill@ grams ot a liquid of the above Formula V, boiling at 265-268 C./0.t)1 mm., DML-21.5947. nalysis of this composition showed it to contain 72.8% carbon, 5.6% hydrogen and to have a molecular weight of 618, as contrasted to the theoretical values of 72.79% carbon, 5.47% hydrogen and a molecular of 627.

EY'iPLE 5 Tile composition l,3di{,8-napl1tliyloxy}-1,l,3,3tetra p? envi disiloxane having the formula VH (75H5 CsHs -a1-0-Sio is prepared similarlyv as aboveby iirst reacting i mole of -napntilol with i mole dipbenyldicblorosilane in pyridine as a bydrohalide acceptor at a temperature of about 0 C. to give f-naplttnyloxy dipbenylcl'llorosilane. This cnlorosilane was tiren hydrolyzedin tbe usual fashion with water to give the abovc-identiiied composition having Formula Vil.

)EXAMPLE 6 The composition l,5di(mnapbtiiyloxy)i,5dipbenyl1, 3,3g5-tetrametbyltrisiionane liaving tbe formula 5 is prepared in the same manner as described in Examples l and 2. More particularly, the a-naplathyloxy phenylmethylclilorosilane required for preparation of the cornposition of Formula Vll is prepared by tbe same procedure as used in Example 1 to prepare o-pbenylpbenox-yphenylmethylchlorosilane, but instead of using o-pbenylphenol, a-naphthoi is used. The obtained a-napiitllyloxyplienylmethylchlorosiiane is hydrolyzed similarly as.

in Example 3 to give the a-naphthyloxymethylphenylsilanol. The latter silanol was then added similarly again as in le 3, to dimetlavlchlorosilane em lo inu die v, P Y s same molar concentrations and the same conditions, to yield the desired composition having Formula VH1.

ln order to determine (by means of an accelerated testytne radiation resistance of the aforesaid compositions in an electron beam which would be the conditions under which these fluids would be expected to operate in tbe above-described projection system, the fluids prepared in the above examples were subjected to electron irradiation with a i500 liv. resonant transformer at a current input of 20G-SSG microamperes at a dose of Ztl-50x10@ roentgens/minute to a total dose of 400 megaroentgens. The following Table I shows the total number of molecules of gas per l0() electron volts absorbed (identied as G gas), as well as the change in viscosity (in centistolres) prior to irradiation (identied as 110, cs.) and ater irradiation (identified as 11, cs.) at tbe temperature at which irradiation was measured.

Table I CS 7i CS- Composition o! Example G gas Temp Viso. Temp., Visc.

50 230 50 313 50 530 50 747 25 900 2.5 1350 25 1GO 25 62B The low gas value and the small change in viscosity under the accelerated test conditions applied to the aboveidentitied compositions as shown in Table I above establisb the eminent suitability of tliese compositions as the deformable medium in place of deformable media disclosed in the aforesaid US. atent 2,943,i47. To iurther establish the usefulness of tbe compositions of the above type, tbe composition of Example 4 was subjected to an electron-raster test using 10 kv. and 2 to 3 microamperes. This test involved subjecting the deformable fluid to constant electron irradiation for a time until irst evidence of gelation (called incipient gel formation) was noted. This is an accelerated, severe test because in the normal use of tlielaforesaid apparatus, tbe deformable medium would be constantly replenished and removed from the zone of irradiation. lt was found that the aforesaid composition wllen subjected to this severe test did not show any incipient gel formation until after mintites, indicating its eminent stability under irradiation conditions.

As a still further test, the compositions of Examples 3 and 4 were used in the normal fashion in the apparatus described in the attached drawing and in US. 2,943,5l47 as the deformable medium recited in the drawing and patent. It was found that sharp, viewable images of good light and color intensity were obtained in each instance.

ln addition to the uses described above, the polysiloranes of Formula I can also be used as hydraulic and dielectric luids Where thermal stability and radiation sista-nce are prerequisites. n sealed systems, the eminent resistance to elevated temperatures recommends these ma terials as hydraulic uids in automobiles and in airplanes.

en fa pioyi as iim dcionmbe n system, it wili 'um in me acov' dem w sinus@ in the com csitions ds where Z and have Liana meanings given above, and 3i is hydroiyzabs grou, f r instance, halogen, auch as coz'ine, bremine, sie. Geneiaiy, liydr-uysis is netted, usually in ihr: presence of a iiydmiiaiide accepor, by ding a sufiicicni amount cf wa 'o sonigtosition of Formula EX to cfec': completa hycioyss le silicn4 bonded 'Liyc'rolyznnlc group.

fi/bcn mailing poiysiloxanc compssitions of in@ present invention having more than two siioxy lnis in 'die noiecuie (auch as illnsfaci in Exe; nies 2 and 3), reaction is advantageously carried out between 2 maize of ille composition 0f Formula i' wiii i anni@ of a puiysiioxane dici of infiniti?,

when: has the: meaning given above and m is a whole mumbai @quai io i o 12. Aicrnaiveiy, suon 00m pssiiun can bs obained by wasting n Qsmpsnnii o ik@ formula XI l? ZO-.i-OBL R RQECig where with a dimganosiiane the ionamin mean! given above.

.-Thc inici-medium compnsions having :im:

muis?.

can be; obtained by reacting i .moin i i mole of a man@ compound oi 'das formula .ELC i diorgzinodichlorosiian (or mixture of ci.. .fgancdicmor siancs) of the form a RZSCIZ whreZ and i2 have die moaning given abavc. lin hose instances where a chiomsiizine is being' reacicd with a silanoi or polysioxanedol, ii is advznitagcous also m employ a. 1\'fc`rniaiid empio? such as pyridine, ertiary amines, etc. The usual inebf ods of fractional disiilation and crysalizaicn'i are @nir manxpes, @thai ploycd using 315: mnhods of @rayman generically and iicaly in mi Jnong auch einer composiions wincln in accordance with the ,pianifica of sempre-Mons Paen of ihr: nited Laien is:

Si. A composition of mamhaving the gcznral formuin i i zo l z f mi when I is a mcmsr seie i .in conS-.isifg of methyl and p lenyl fad c is a 3 (tied rorn die ciass consiscing o e noxyphenyl radicals and lim e nuinwi' @Quai in from 2 to fe', inclusive.

Z. A coznpssition of matr having f :mi a.

g Hg Ha En 5. A compcsiion of maie having 'ha ormuia ons (13511:

7. A projection system comprising a container having a conducting interior, a deormabie medium in said conrainer comprising a composition having tile formula v i l zo--sIa-OT R Jn where is a member selected from tile class consisting of the metiryl radical and phenyl radical, Z is a member seiected from tlie ciass consisting oic tine bipbenylyl, phenoxyphenyl, and naphtlayl radicals, .n is a whole num- 'oer equai to from 2 to 4, inciusive, an electron beam means :For producing an electrical ciiarge on tine surface of said deformable medium as a function of an applied electrical signal and cooperating with said conducting interior io subject the medium to a defer-ming force to produce deformations on the surface of said medium, and a iight and opicai system for projecting light as a function of the deformations in the surface of said medium.

A projection system comprising a container having a conducting interior, e deformable medium in said container comprising a composition having the formula an electron beam means for producing an electrical charge on the surface of said deformable medium as a, function or an applied eiectrical signal and cooperating with said conducting interior to subject the medium 'to a deforming force to produce deformations in the sur face of said medium, and a light and optical system for projecting light as a function of the deformations in the surface of said medium.

9. A projection system comprising a container having a conducting interior, a deformable medium in said container comprising a composition iiaving the forrnuia adsense an electron beam means for producing an electrical charge on the surface of said deformable medium as a function of an applied electrical signal and cooperating'v with said conducting interior to subject the medium to a deforming force to produce deformations in the surface of said medium, and a light and optical system for projecting light as a function of the deformations in the Surface of said medium.

10. A projection system comprising a container having, a conducting interior, a deformable medium in said container comprising a composition having the formula an electron beam means for producing an electricai charge on the surface of said deforinabie medium as a function of an applied electrical signal and cooperating with said conducting interior to subject the medium to a deforming force to produce deformations in the surq face of said medium, and a light and optical system `rior projecting light as a function of the deformations in tile surface of Said medium.

il. A projection system comprising a container having a conducting interior, a deformable medium in said con tainer comprising a composition having the formula an electron beam means for producing an electricai charge on the surface of said deformable medium as a function of an appiied electrical signal and cooperating with said conducting interior to subject the medium to a deforming force to produce deformations in tire surf face of said medium, and a iigii and optical system for projecting iight as a function or" the deformations in the surface of said medium.

No references cited. 

7. A APROJECTION SYSTEM COMPRISING A CONTAINER HAVING A CONDUCTING INTERIOR, A DEFORMABLE MEDIUM IN SAID CONTAINER COMPRISING A COMPOSITION HAVING THE FORMULA 